Home Physical Sciences The crystal structure of one-dimensional cooridnation polymer bis(thiocyanato)-bis((1E,2E)-1,2-bis(1-(pyridin-3-yl)ethylidene)-hydrazine κ2N:N)iron(II), (C30H28N10S2Fe)n
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The crystal structure of one-dimensional cooridnation polymer bis(thiocyanato)-bis((1E,2E)-1,2-bis(1-(pyridin-3-yl)ethylidene)-hydrazine κ2N:N)iron(II), (C30H28N10S2Fe)n

  • Tong Cao and Daopeng Zhang ORCID logo EMAIL logo
Published/Copyright: October 23, 2025

Abstract

C30H28N10S2Fe, monoclinic, P21/n (no. 14), a = 9.5643(4) Å, b = 16.9693(9) Å, c = 9.5997(5) Å, β = 98.531(5)°, V = 1540.79(13) Å3, Z = 2, R gt (F) = 0.0457, wR ref (F2) = 0.1316, T = 293 K.

CCDC no.: 2493477

The molecular structure is shown in the figure. Table 1 contains the crystallographic data and the list of the atoms including atomic coordinates and displacement parameters can be found in the cif-file attached to this article.

Table 1:

Data collection and handling.

Crystal: Yellow block
Size: 0.20 × 0.14 × 0.08 mm
Wavelength: Mo Kα radiation (0.71073 Å)
μ: 0.66 mm−1
Diffractometer, scan mode: Bruker APEX2, φ and ω scans
θmax, completeness: 25.0°, 100 %
N(hkl)measured, N(hkl)unique, Rint: 5666, 2716, 0.026
Criterion for Iobs, N(hkl)gt: Iobs > 2 σ(Iobs), 2280
N(param)refined: 198
Programs: Bruker, 1 SHELX 2 , 3

1 Source of materials

The ligand (1E,2E)-1,2-bis(1-(pyridin-3-yl)ethylidene)-hydrazine (L1) was synthesized according to the literature method. 4 The ligand L1 (47.6 mg, 0.2 mmol) disolved in methanol solution (10 mL) was carefully mixed with another methanolic solution (10 mL) containing KSCN (19.4 mg, 0.2 mmol) and anhydrous FeCl2 (12.7 mg, 0.10 mmol). The resulted solution was stirred for a few minutes and, after filteration, the filterate was allowed to slowly evaporate in the dark with no disturbance in air at room temperature. Yellow block crystals, obtained after several days were collected and air-dried. Yield: 41.6 mg (64.14 %).

2 Experimental details

Coordinates of hydrogen atoms bonded to the C atoms were refined with constraints or restraints. Their Uiso values were set to 1.2Ueq or 1.5Ueq of the parent atoms.

3 Comment

Iron(II)-based spin crossover (SCO) complexes, which have been given intense attention due to their easily spin transition behavior between the paramagnetic high-spin (HS) state t2g4eg2 (S = 2) and the diamagnetic low-spin (LS) t2g6eg0 (S = 0) under the external stimuli (temperature, pressure, light irradiation, guest molecules, and so on), 5 , 6 , 7 are with various structure types ranging from zero-dimensional clusters to three-dimensional networks. Among of the organic ligands used, due to their moderate coordination ability suitable for tuning the spin state of the central Fe(II) ion, many research have devoted to developing new SCO material with multi-dimensional structure by employing the bispyidine-like compounds as auxiliary ligands. In this paper, we report the structure of a new one-dimensional Fe(II) complex based on a semi-rigid bidentate pyridine-type ligand L1, which has been successfully used to prepare the 1D Cd(II), Co(II), Zn(II) and Cu(II) complexes. 8 , 9 , 10 , 11

As shown in figure, the title neutral Fe(II) complex [ Fe L 1 2 NCS 2 ], which contains two units in the unit cell similar to above mentioned complexes, 8 , 9 , 10 , 11 belongs to loop-like one-dimensional chain structure. The Fe(II) ion in the title complex is involved in octahedral coordination geometry, in which the four equatorial sites were occupied by the four N atoms of L1 acting as bidentate bridging ligands and two axial positions were coordinated by two N atoms of the thiocyanato ions as terminal ligands. The Fe–N L 1 and Fe–NNCS bond lengths are 2.238(3), 2.253(3) and 2.091(3) Å, respectively, which are basically consistent with the corresponding values found in reported Fe(II) complexes based-on the analogue of L1, 6 , 12 demonstrating the slightly distorted octahedral sphere of the central Fe(II) ion and implying also the paramagnetic high spin state nature of the Fe(II) ion. The Fe–NC bond angle is 167.1(3)°, indicating the slight deviation from the linear conformation of these three atoms. Indeed, the angle parameter corresponding to deviations from the ideal octahedron of the 12 cis bond angles is 58.5° at room temperature, markedly larger than the corresponding value in the low spin Fe(II) complex with the metal center being involved in a comparative regular octahedron, 13 further proving the high spin state of the central Fe(II) ion.


Corresponding author: Daopeng Zhang, College of Chemistry and Chemical Engineering, Shandong University of Technology, Zibo 255049, P.R. China, E-mail:

Acknowledgments

We gratefully acknowledge support by the Natural Science Foundation of China (22171166 and 22211530417).

References

1. Bruker. Apex2, Saint-Plus, Xprep; Bruker AXS Inc.: Madison, Wisconsin, USA, 2004.Search in Google Scholar

2. Sheldrick, G. M. Shelxt – Integrated Space-Group and Crystal-Structure Determination. Acta Crystallogr. 2015, A71, 3–8; https://doi.org/10.1107/s2053273314026370.Search in Google Scholar PubMed PubMed Central

3. Sheldrick, G. M. Crystal Structure Refinement with Shelxl. Acta Crystallogr. 2015, C71, 3–8; https://doi.org/10.1107/s2053229614024218.Search in Google Scholar

4. Dong, Y. B.; Smith, M. D.; zur Loye, H. C. New Inorganic/Organic Coordination Polymers Generated from Bidentate Schiff-base Ligands and Metal Nitrate Hydrates (M = Cd(II), Co(II)). Inorg. Chem. 2000, 39, 4927–4935; https://doi.org/10.1021/ic0006504.Search in Google Scholar PubMed

5. Chen, X. Q.; Cai, Y. D.; Jiang, W.; Peng, G.; Feng, J. K.; Liu, J. L.; Tong, M. L.; Bao, X. A Multi-Stimuli-Responsive Fe(II) SCO Complex Based on an Acylhydrazone Ligand. Inorg. Chem. 2019, 58, 999–1002; https://doi.org/10.1021/acs.inorgchem.8b02922.Search in Google Scholar PubMed

6. Yang, F. L.; Chen, M. G.; Li, X. L.; Tao, J.; Huang, R. B.; Zheng, L. S. Two-Dimensional Iron(II) Networks-Guest-Dependent Structures and Spin-Crossover Behaviors. Eur. J. Inorg. Chem. 2013, 4234–4242; https://doi.org/10.1002/ejic.201300211.Search in Google Scholar

7. Zhang, L. Q.; Tong, Y. F.; Kelai, M.; Bellec, A.; Lagoute, J.; Chacon, C.; Girard, Y.; Rousset, S.; Boillot, M. L.; Rivière, E.; Mallah, T.; Otero, E.; Arrio, M. A.; Sainctavit, P.; Repain, V. Anomalous Light-Induced Spin-State Switching for Iron(II) Spin-Crossover Molecules in Direct Contact with Metal Surfaces. Angew. Chem., Int. Ed. 2020, 59, 13341–13346; https://doi.org/10.1002/anie.202003896.Search in Google Scholar PubMed

8. Dang, D. B.; Guo, X. Y.; Bai, Y.; Gao, H.; Zhang, G. Q. Synthesis, Crystal Structure and Luminescent Properties of One Cadmium(II) Coordination Polymer with Mixed Imine-based Bidentate Schiff-base and Thiocyanate Ligands. Synth. React. Inorg., Met-Org., Nano-Met. Chem. 2010, 40, 195–199; https://doi.org/10.1080/15533171003629154.Search in Google Scholar

9. Dong, Y. B.; Smith, M. D.; zur Loye, H. C. New Inorganic-Organic Coordination Polymers Generated from Rigid or Flexible Bidentate Ligands and Co(NCS)2…xH2O. J. Solid State Chem. 2000, 155, 143–153; https://doi.org/10.1006/jssc.2000.8915.Search in Google Scholar

10. Khanpour, M.; Morsali, A. Solid State Crystal-to-Crystal Transformation from a Monomeric Structure to 1-D Coordination Polymers on Anion Exchange. CrystEngComm 2009, 11, 2585–2587; https://doi.org/10.1039/b908362f.Search in Google Scholar

11. Dang, D. B.; Li, M. M.; Bai, Y.; Wang, J. L. Two One-Dimension Copper(II) Coordination Polymers Based on Imine-based Bidentate Schiff-base Ligand: Synthesis, Crystal Structure and Luminescent Properties. Spectrochim. Acta Mol. Biomol. Spectrosc. 2011, 83, 499–503; https://doi.org/10.1016/j.saa.2011.08.073.Search in Google Scholar PubMed

12. Zhang, D. P.; Valverde-Munoz, F. J.; Bartual-Murgui, C.; Pineiro-Lopez, L.; Carmen Muñoz, M.; Real, J. A. {[Hg(SCN)3]2(μ–L)}2−: an Efficient Secondary Building Unit for the Synthesis of 2D iron(II) spin-crossover Coordination Polymers. Inorg. Chem. 2018, 57, 1562–1571, https://doi.org/10.1021/acs.inorgchem.7b02906.Search in Google Scholar PubMed

13. Xu, Z.; Meng, S.; Cao, T.; Xin, Y.; Wang, C.; Hao, H.; Yang, L.; Zhou, Z.; Zhang, D. Substituent Group Tuned Structural Dimensionalities and Magnetic Properties of V-Shaped bis-pyridyl Ligands Based Fe(II) Coordination Polymers. J. Mol. Struct. 2024, 1296, 136866; https://doi.org/10.1016/j.molstruc.2023.136866.Search in Google Scholar

Received: 2025-08-09
Accepted: 2025-10-06
Published Online: 2025-10-23
Published in Print: 2025-12-17

© 2025 the author(s), published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution 4.0 International License.

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